US5681468A - Filter coated with antimicrobial material - Google Patents
Filter coated with antimicrobial material Download PDFInfo
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- US5681468A US5681468A US08/599,810 US59981096A US5681468A US 5681468 A US5681468 A US 5681468A US 59981096 A US59981096 A US 59981096A US 5681468 A US5681468 A US 5681468A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/24—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients to enhance the sticking of the active ingredients
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
- A01N47/44—Guanidine; Derivatives thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
- B01D39/2027—Metallic material
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0069—Inorganic membrane manufacture by deposition from the liquid phase, e.g. electrochemical deposition
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- B01D67/0039—Inorganic membrane manufacture
- B01D67/0072—Inorganic membrane manufacture by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B01D69/12—Composite membranes; Ultra-thin membranes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/02—Inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/02—Inorganic material
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- B01D71/0223—Group 8, 9 or 10 metals
- B01D71/02231—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
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- B01D71/02—Inorganic material
- B01D71/022—Metals
- B01D71/0223—Group 8, 9 or 10 metals
- B01D71/02232—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
- B05B11/01—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use characterised by the means producing the flow
- B05B11/04—Deformable containers producing the flow, e.g. squeeze bottles
- B05B11/047—Deformable containers producing the flow, e.g. squeeze bottles characterised by the outlet or venting means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D47/00—Closures with filling and discharging, or with discharging, devices
- B65D47/04—Closures with discharging devices other than pumps
- B65D47/06—Closures with discharging devices other than pumps with pouring spouts or tubes; with discharge nozzles or passages
- B65D47/18—Closures with discharging devices other than pumps with pouring spouts or tubes; with discharge nozzles or passages for discharging drops; Droppers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
- A61J1/14—Details; Accessories therefor
- A61J1/1443—Containers with means for dispensing liquid medicaments in a filtered or sterile way, e.g. with bacterial filters
- A61J1/145—Containers with means for dispensing liquid medicaments in a filtered or sterile way, e.g. with bacterial filters using air filters
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
- A61J1/14—Details; Accessories therefor
- A61J1/1443—Containers with means for dispensing liquid medicaments in a filtered or sterile way, e.g. with bacterial filters
- A61J1/1456—Containers with means for dispensing liquid medicaments in a filtered or sterile way, e.g. with bacterial filters using liquid filters
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
- A61J1/14—Details; Accessories therefor
- A61J1/1468—Containers characterised by specific material properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0442—Antimicrobial, antibacterial, antifungal additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0471—Surface coating material
- B01D2239/0478—Surface coating material on a layer of the filter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
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- B01D2325/48—Antimicrobial properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
Definitions
- the present invention relates to liquid dispensers, specifically, the provision of liquid dispensers capable of maintaining sterile solutions during storage, during dispensing, and subsequent to dispensing of the solution, as well as methods of manufacture and use of such dispensers.
- Single dose dispensers are available. Such dispensers, however, are made only for one time use, and are then discarded, adding considerably to packaging costs. Moreover, more sterile solution than is required for a single dose is usually packaged which also adds to the expense of the treatment. Another problem is that persons may attempt to use the single dose dispenser multiple times, which can result in contaminated liquid being dispensed.
- preservatives have been added to multi-dose dispensers to prevent microbial contamination after the dispenser is initially used.
- Such preservatives are often toxic to mammalian cells, as well as microbial cells.
- many preservatives used in eye drop formulations are toxic to the goblet cells in the eye. Such toxicity is detrimental to persons requiring prolonged application of the solutions.
- Membrane filters have also been used in liquid dispensers in attempts to prevent microbial contamination of the stored sterile liquid. If a hydrophilic filter is used, however, the filter can allow the phenomenon known as "grow-through,” in which microbial progeny on the downstream (non-sterile) side of the filter can pass through the filter pores because of their smaller size during cell division, and thereby contaminate the sterile solution contents in the dispenser.
- Hydrophobic filters have also been employed in liquid dispensers. Hydrophobic surfaces are non-wetting, and therefore are significantly more difficult for microbes to grow on. Such filters, however, because of their hydrophobicity will not allow the flow of sterile aqueous solutions through the filter.
- a metal e.g., silver
- a metal e.g., silver
- Still another object of the invention is to provide a liquid dispenser for sterile liquids which is economical, efficient and durable.
- a liquid dispenser e.g., a multi-dose dispenser, for dispensing a sterile liquid.
- the liquid dispenser has a container for storing the sterile liquid and a nozzle assembly which is mounted on the container.
- the nozzle assembly has a passageway which enables the sterile liquid to flow from the container through the passageway when the liquid is dispensed.
- the liquid dispenser also has a filter which is attached to the nozzle assembly so that the filter extends across the passageway to direct liquid and air flow through the filter from the container to the downstream surface of the filter.
- the filter e.g., an organic filter or inorganic filter
- a metallic material e.g., a metal such as silver, or a metal oxide, or a metal salt, or mixtures thereof, that is bacteriostatic or bacteriocidal.
- the filter has pores of a size, e.g., approximately 0.1 microns to approximately 1.2 microns, preferably, approximately 0.22 microns to approximately 0.65 microns, which preclude passage of microorganisms through the filter, and permit passage of the sterile liquid from the container through the filter.
- the filter is also at least partially coated within a plurality of its pores with the metallic material. Variations include the upstream surface of the filter also being at least partially coated with the metallic material.
- variations are the surfaces and plurality of pores of the filter being at least partially coated with an additional different metallic material that is bacteriostatic or bacteriocidal.
- a variation is the liquid dispenser having a second filter that is serially aligned with the first metal coated filter, and which is at least partially coated on at least one surface and within a plurality of its pores with a different metallic material that is bacteriostatic or bacteriocidal.
- the filter and a plurality of the pores which are coated with one or more metallic materials can have at least a partial additional coating with a compound that has an anti-viral or anti-bacterial property.
- the filter includes a hydrophobic portion for allowing air to enter the container to replace the sterile liquid that is dispensed from the filter dispenser.
- the passageway walls in the nozzle assembly, at least on the downstream side of the filter are coated with a metallic material that is bacteriostatic or bacteriocidal.
- the liquid dispenser can have a prefilter which is spaced upstream from the filter for providing a barrier to the passage of particulate matter through the prefilter and for permitting the passage of sterile liquid from the container through the prefilter.
- a support means can also be spaced upstream from the filter for reinforcement of the filter.
- a dispenser for dispensing sterile liquids which has a filter attached to a container for liquids, the improvement being the filter being at least partially coated on the downstream surface with a metallic material that is bacteriostatic or bacteriocidal; the filter extending across a passageway provided by the container leading from the container to a dispensing area where the liquid is dispensed; the filter having pores with a pore size so as to preclude passage of microorganisms therethrough and so as to permit passage of sterile liquid from the container therethrough; and the filter also being at least partially coated within a plurality of the pores with the metallic material.
- Yet another aspect of the invention features a filter having pores providing liquid conduits interconnecting the upstream and downstream surfaces of the filter for liquid passage from one of the surfaces to the other.
- the pores are of a size so as to preclude passage of microorganisms through the filter and so as to permit passage of liquid and air through the filter.
- At least one surface of the filter is at least partially coated with a metallic material, e.g., a metal such as silver, or a metal oxide, or a metal salt, or mixtures thereof, that is bacteriostatic or bacteriocidal, and the filter further is at least partially coated within a plurality of the pores with the metallic material.
- Variations include the upstream surface also being at least partially coated with the metallic material.
- the filter surfaces and a plurality of the pores can be at least partially coated with an additional metallic material that is bacteriostatic or bacteriocidal, and/or a different compound that has an anti-viral or anti-bacterial property.
- the invention also includes a method in which a sterile liquid can be dispensed by applying pressure to the container of the liquid dispenser of this invention so as to discharge the sterile liquid from the container.
- the container preferably is formed at least in part of a resiliently deformable material, such as an elastic polymer, which permits manual squeezing, e.g., to discharge a dose of medicament, and subsequent elastic recovery of the material to its original configuration by drawing gas from a surrounding atmosphere into the container while the gas is sterilized by the filter in passing therethrough.
- the liquid dispenser is used for eyecare in an organism, in which a sterile eyecare liquid, e.g., liquid artificial tears, a solution for contact lens care or a medicament, is dispensed from the liquid dispenser into the eye or onto an object that is to be placed into the eye.
- a sterile eyecare liquid e.g., liquid artificial tears, a solution for contact lens care or a medicament
- the eyecare liquid is preservative-free.
- the invention also features a method for coating the surface and pores of a filter with a metal by providing a filter with pores, contacting the filter with a carbonyl compound, e.g., an aldehyde such as glutaraldehyde, a sugar such as glucose, or an aldehyde functionality generating compound, drying the filter, contacting the dried filter with a metal salt, e.g., silver nitrate, or metal carboxylate salt solution, e.g., silver tartrate, and an amine-containing compound solution, e.g., ammonium hydroxide, so as to deposit the metal on the surface and within a plurality of the pores of the filter.
- a carbonyl compound e.g., an aldehyde such as glutaraldehyde, a sugar such as glucose, or an aldehyde functionality generating compound
- a metal salt e.g., silver nitrate, or metal carboxylate salt solution, e.g., silver tartrate
- a filter having pores is provided, the filter is contacted with an activator, e.g., tin dichloride, the filter is dried, and the filter is contacted with a metal salt or metal carboxylate salt solution, either with or without an amine-containing compound solution, so as to deposit the metal on the surface and within a plurality of the pores of the filter.
- an activator e.g., tin dichloride
- a metal salt or metal carboxylate salt solution either with or without an amine-containing compound solution
- FIG. 1 is a semi-diagrammatic cross-sectional view of a liquid dispenser in accordance with the present invention.
- FIG. 2 is a semi-diagrammatic cross-sectional view of an upper portion of the liquid dispenser of FIG. 1
- FIG. 3 is a semi-diagrammatic top view taken through line 25-25 of FIG. 2 showing the concentric and radial channels of the invention.
- FIGS. 1-3 provides a liquid dispenser 1 for dispensing a sterile liquid 2.
- the liquid dispenser 1 has a container 4 for storing sterile liquid 2 and a nozzle assembly 3 which is mounted on top of container 4.
- Nozzle assembly 3 has a passageway 5 which enables sterile liquid 2 to flow from container 4 through passageway 5 when sterile liquid 2 is dispensed.
- Container 4 is designed to permit manual squeezing so as to force sterile liquid 2 from container 4 through filter 6 out of orifice 7 of nozzle assembly 3. In normal operation, liquid dispenser 1 is inverted and container 4 is squeezed.
- Container 4 as shown in FIG. 1, has a circular cross-section extending along a vertical axis 8, with a flat bottom 9 and an upper end 10.
- Sidewall thickness is preferably in the range of 0.01 to 0.25 inch.
- the shape of the container can be round, elliptical, polygonal, irregular, or the like, and in some cases may be in tube form.
- the particular sidewall thickness can vary greatly, as can the volume of the chamber within container 4 that holds the medicament or other liquid to be dispensed. Thus, various sizes ranging from cubic millimeters to cubic centimeters or more can be used for the container chamber.
- the nozzle assembly 3 is an ovoid form.
- the nozzle assembly has a cross-section formed of a plastic material which is self-supporting and defines a generally ovoid configuration having an inverted lip portion 11 mating with and sealed to the top of container 4 at upper end 10.
- Nozzle assembly 3 includes within it a ring-shaped lower spacer 12 of a solid material having a central passage connecting the chamber of container 4 with the filter or filters and an upper spacer 13 which acts to hold the filter or filters in place.
- the lower spacer 12 comprises a supporting screen 30.
- a disc 14 carries channel means. As shown in FIG.
- disc 14 carries a plurality of concentric channels 22 which are interconnected by radial channels 23 to a central passageway 5 so that liquid coming from container 4 will pass through the filter or filters and be distributed on the surface of disc 14 so as to cause dispensed sterile liquid 2 to coalesce into a single drop or a stream of liquid when expelled from container 4.
- Disc 14 is held in place by being adhesively secured, e.g., by ultrasonic welding or by a mechanical force, to the upper spacer 13.
- Support 16, prefilter 15, filter 6 and second filter 17 can be suspended by spacers 12 and 13. In some embodiments, only filter 6 need be used and one or more of the support, prefilter or second filter, can be eliminated. Various combinations of these elements can be used in different embodiments as desired.
- prefilter and filter as well as the second filter, are shown as planar members, various configurations can be used. These members can be in the form of cones, polygonal or other shaped devices as may be desirable for specific applications. Planar sheet-type materials as shown are preferred.
- passageway 5 is preferably axially extending with a circular cross-section, it can have any configuration as desired for specific applications.
- Container 4 can be formed, e.g., from a flexible material, e.g., an elastically deformable polymer, e.g., thermosetting or thermoplastic polymeric material, e.g., polypropylene, polyethylene, polyvinylchloride, polyethylene terephthalate, polytetrafluoroethylene, polysulfone and polyethersulfone.
- a flexible material e.g., an elastically deformable polymer, e.g., thermosetting or thermoplastic polymeric material, e.g., polypropylene, polyethylene, polyvinylchloride, polyethylene terephthalate, polytetrafluoroethylene, polysulfone and polyethersulfone.
- the container can be a deformable metallic or plastic medicament container, such as a toothpaste tube, where the container may remain deformed after each dose is dispensed.
- Nozzle assembly 3 can be formed from the same or a more rigid type of material than container 4.
- nozzle assembly 3 is permanently attached to container 4 with a liquid-tight connection so as to aid in maintaining sterility of sterile liquid 2 in container 4.
- a connection can be formed by standard techniques, e.g., ultrasonic welding, heat press sealing, adhesive sealing or mechanical sealing.
- Filter 6 is sealingly attached to nozzle assembly 3 so that filter 6 extends across the entire expanse of passageway 5 to direct liquid and air flow out of and into container 4 through filter 6.
- Filter 6 can be attached to nozzle assembly 3 by any method which results in such a seal, including, e.g., ultrasonic sealing, heat press sealing and adhesive sealing.
- filter any material which can function as a microbial filter, e.g., membranes.
- the filter of this invention includes, e.g., organic and inorganic filters.
- Organic filters include, e.g., any polymeric material which can be used for the preparation of membranes or filter papers. Examples of organic filters include polysulfone, polyethersulfone, polyamide, e.g., nylon, polycarbonate, polyacrylate, polyvinylidene fluoride, polyethylene, polypropylene, cellulosics, e.g., cellulose, and Teflon®.
- any of the hydrophobic materials require prior activation with techniques such as plasma, chemical oxidation or metallic sensitization, e.g., a primer.
- Inorganic filters include, e.g., glass fiber filter paper, ceramic membranes, e.g., alumina or silica, and metal filters. Sintered glass and sintered ceramic blocks can also be used.
- the filters can be either hydrophilic or hydrophobic. If a hydrophobic filter is used, the metal coating, described below, converts it to a filter with hydrophilic properties.
- Filter 6 has pores which form interconnecting liquid conduits extending from an upstream surface of the filter to a downstream surface.
- the pore size for filter 6 is chosen so that the pores permit passage of sterile liquid 2 from container 4 through filter 6, but preclude passage of microorganisms through filter 6, thereby maintaining the sterility of sterile liquid 2 in container 4.
- microorganism is meant bacteria, blue-green algae, fungi, protozoa and algae.
- the pore size can range, e.g., from approximately 0.1 microns to approximately 1.2 microns.
- the pore size is approximately 0.22 microns to approximately 0.65 microns.
- the pore size is 0.65 microns.
- this invention can produce a sterile filtrate with larger pore sizes, e.g., 0.45 and 0.65 microns, thus permitting a device which gives a faster flow rate for the dispensed liquid.
- a major problem in multi-dose liquid dispensers is that liquid may accumulate downstream of the filter subsequent to dispensing liquid from the container.
- downstream of the filter is meant that it is on the side of the filter that liquid from the container which has passed through the filter would be on, e.g., the surface of the filter exposed to the outside atmosphere.
- upstream of the filter is meant that it is on the side of the filter that liquid from the container which has not yet passed through the filter would be on.
- Microorganisms can multiply in this accumulated downstream liquid which can contaminate subsequent drops which are dispensed and which come into contact with the accumulated liquid on the downstream side of the filter.
- certain microorganisms in this accumulated liquid can, because of their smaller size during cell division, pass through the pores of the filter, a phenomenon known as "grow-through," and contaminate the sterile liquid upstream of the filter.
- bacteriocidal is meant the killing of microorganisms.
- bacteriostatic is meant inhibiting the growth of microorganisms which can be reversible under certain conditions.
- a metallic material that is bacteriostatic or bacteriocidal is meant a metallic material that is bacteriostatic to a microorganism, or that is bacteriocidal to a microorganism, or that is bacteriocidal to certain microorganisms and bacteriostatic to other microorganisms.
- filter 6 is also at least partially coated on the upstream surface with a metallic material, e.g., a metal or metal oxide or metal salt or mixtures thereof.
- a metallic material e.g., a metal or metal oxide or metal salt or mixtures thereof.
- Any metal which is bacteriostatic or bacteriocidal can be used. Examples of such metals include, e.g., silver, zinc, cadmium, mercury, antimony, gold, aluminum, copper, platinum and palladium.
- the appropriate metal coating is chosen based upon the use to which the sterile liquid passing over the metal coated filter is to be put.
- metals which are not toxic are coated on filters which are to be used for filtering solutions that are to be applied to humans and other organisms.
- the preferred metal is silver.
- filter 6 has both hydrophilic and hydrophobic regions.
- a hydrophobic filter which has only been coated with a metal or metal oxide or metal salt on a portion of the filter, will be hydrophilic for the coated portion and hydrophobic for the uncoated portion.
- a hydrophilic or hydrophobic filter is coated with a metal, metal oxide or metal salt, so as to make the filter hydrophilic, and then a portion of this metallic surface is rendered hydrophobic by the incorporation of a hydrophobic coating, e.g., an alkyl mercaptan such as octyl mercaptan.
- Such a dual purpose filter is preferred when multiple doses of liquid are dispensed in quick succession to each other, in order to more quickly replace the liquid which has been dispensed from the container with air from outside the container, so as to equalize the pressure.
- the dispensed liquid can pass through the hydrophilic portion of the filter, and the replacement air can pass through the hydrophobic portion without being hampered by the presence of liquid on the hydrophilic portion.
- an air port or vent (not shown) can be provided through upper spacer 13 so as to allow air passage to container 4 as the liquid is dispensed from container 4.
- the air port or vent provides for compensation of the air pressure as liquid is dispensed from the container so as to avoid formation of a vacuum.
- the device will work with or without the air port or vent, however, if a constant and sustained flow is desired, better flow rates may be obtained with the use of an air port or vent.
- the air port or vent described may be particularly desirable to equalize pressure as liquids leave the container. In such a case, it is preferred that the air port or vent be positioned above the hydrophobic portion of the filter.
- the invention also provides for a filter in which the downstream surface and a plurality of the pores are at least partially coated with an additional second metallic material, e.g., a metal or metal oxide or metal salt or mixtures thereof, that is bacteriostatic or bacteriocidal.
- the upstream surface is also at least partially coated with the second metal or metal oxide or metal salt.
- metals that can be used are discussed above in relation to the single metal coating.
- the use of two different metals can enhance the anti-microbial properties of the filter. Different types of microorganisms can exhibit different degrees of sensitivity to different metals.
- the use of two different metals can significantly reduce the problem of selection for microorganisms having resistance to the metal in the metal coating that can occur when only one metal is used.
- Another variation of the invention is a liquid dispenser which has a second filter 17 with pores of a size that permits passage of sterile liquid 2 from container 4, that is serially aligned with filter 6.
- Second filter 17 is at least partially coated on at least one surface and within a plurality of its pores with a different metallic material, e.g., a metal or metal oxide or metal salt or mixtures thereof, that is bacteriostatic or bacteriocidal, than is used for the coating on filter 6.
- a different metallic material e.g., a metal or metal oxide or metal salt or mixtures thereof, that is bacteriostatic or bacteriocidal
- the presence of different metals on different filters in the liquid dispenser is advantageous for the same reasons as discussed above regarding the embodiment where two different metals are applied to a single filter. In other embodiments, more than two different metal or metal oxide or metal salt coated filters are present.
- the downstream surface of the filter and a plurality of pores of the filter, which are coated with one or more metals or metal oxides or metal salts has at least a partial additional coating with a compound that has an anti-viral or anti-bacterial property.
- anti-viral is meant capable of killing, or suppressing the replication of, viruses.
- anti-bacterial is meant bacteriostatic or bacteriocidal.
- Such a compound can be non-metallic.
- This additional coating can allow for more effective anti-bacterial liquid dispensers, in that different anti-bacterial compounds can exhibit different degrees of effectiveness for different types of microorganisms. Multiple anti-bacterial compounds also significantly reduce the problem of selection for microorganisms having resistance to the metal in the metal coating, as discussed above.
- this additional coating can allow for joint anti-bacterial/anti-viral liquid dispensers.
- this compound is bound as a monolayer to at least a portion of the metal coating on the filter.
- Any compound which has anti-bacterial or anti-viral activity can be used. Examples of such compounds include, e.g., benzalkoniumchloride thiol, (the synthesis of which is described in Example 9), polycationic compounds, e.g., ⁇ -4- 1-tris(2-hydroxyethyl) ammonium-2-butenyl!
- poly 1-dimethylammonium-2-butenyl!- ⁇ -tris(2-hydroxyethyl) ammonium chloride and biguanides of the general formula: ##STR1## or their water soluble salts, where X is any aliphatic, aromatic, substituted aliphatic or aromatic, or a mixture of any of these, and Y 1 and Y 2 are any aliphatic, aromatic, substituted aliphatic or aromatic, or a mixture of any of these, and where n is an integer equal to or greater than 1, e.g., chlorhexidine or polyhexamethylene biguanide (available from Zeneca of Wilmington, Del.). These compounds are modified to include a thiol group in their structure so as to allow for the bonding of the compound to the metallic surface of the filter.
- the invention also includes an embodiment in which the liquid dispenser has a prefilter 15 which is spaced upstream from filter 6 and provides a barrier to the passage of particulate matter through prefilter 15, while permitting passage of sterile liquid 2 from container 4 through prefilter 15.
- the pore size of prefilter 15 is approximately 1 micron to approximately 50 microns.
- the prefilter material includes, e.g., glass fibers, synthetic polymer fibers, e.g., hydrophilic polypropylene fibers, nylon and cellulosic fibers.
- prefilter 15 is attached to filter 6 in embodiments where there is only one filter, or attached to the most upstream filter where there is more than one filter, and is also attached to nozzle assembly 3.
- the attachments are by welding.
- the liquid dispenser has a support 16 which is spaced upstream from the filter to act as a reinforcement for the filter.
- support 16 is perforated.
- Support 16 can be made from any material that the container or nozzle assembly is made from.
- the internal walls 18 of nozzle assembly 3 are at least partially coated with a metallic material, e.g., a metal or metal oxide or metal salt or mixtures thereof, that is bacteriostatic or bacteriocidal.
- a metallic material e.g., a metal or metal oxide or metal salt or mixtures thereof.
- a surface and pores of a filter are coated with a metal.
- a filter having pores is provided, the filter is contacted with a carbonyl compound, the filter is dried, and the dried filter is contacted with a metal salt solution or metal carboxylate salt solution and an amine-containing compound solution so as to deposit the metal on the surface and within a plurality of the pores. In one embodiment, this filter is then washed and dried.
- the filter can be any of the filters described above.
- the carbonyl compound includes, e.g., aldehydes, sugars, and aldehyde functionality generating compounds.
- Aldehydes include compounds with the formula R(CHO) n , where R is any aliphatic, aromatic or heteroaromatic group and n is an integer greater or equal to 1.
- water soluble aldehydes are glutaraldehyde, formaldehyde, acetaldehyde, butyraldehyde, glyceraldehyde, glyoxal, glyoxal disodium bisulfite, paraldehyde and cyclic trioxanes.
- water insoluble aldehydes are cinnamaldehyde and benzaldehyde.
- sugar is meant a reducing sugar.
- Sugars include, e.g., fructose, glucose, lactose, maltose and galactose.
- aldehyde functionality generating compound it is meant a compound capable of generating aldehyde group(s). Examples of such compounds include acetals and hemiacetals. Polymeric acetals, e.g., paraformaldehyde and polyacetal, can also be used in this invention.
- the carbonyl compound acts as a reducing agent, so that the metal ion is reduced to the metal, e.g., silver ion is reduced to metallic silver.
- This electroless redox reaction occurs in situ in solution or in the solid state.
- the carbonyl compound has affinity for aqueous and non-aqueous phases and therefore can be used in the process of coating either hydrophilic or hydrophobic filters. If hydrophobic filters are used, the resulting metal coating confers hydrophilic properties on the coated filter.
- the filter After treatment with the carbonyl compound, the filter is either immersed directly into the metal salt solution or metal carboxylate salt solution, or is dried first and then immersed in this solution. Preferably, the filter is first dried. The drying step increases the metal coating within the pores of the filter and produces a more uniform metal coating thickness on the surface and within the pores of the filter. Coating within the pores enhances the bacteriostatic or bacteriocidal properties of the filters.
- any metal which has bacteriostatic or bacteriocidal properties, as described above, can be used in this invention to coat the filters.
- the metal is silver.
- the silver salts that can be used in the metal coating process are salts that are capable of solubilizing, even to a limited degree, in aqueous media, to produce silver ions. Such salts include, e.g., silver nitrate, silver benzoate, silver tartrate and silver acetate, silver citrate or any silver carboxylate.
- Metal carboxylate salts include compounds with the formula R(COO - M + ) n , where R is any aliphatic, aromatic or heteroaromatic group and n is an integer greater or equal to 1.
- metal carboxylate salts include, e.g., silver, zinc, cadmium, mercury, antimony, gold, aluminum, copper, platinum and palladium salts of acetic, propanoic, lactic or benzoic acid; and mono-or di-sodium or potassium salts of diacids, e.g., oxalic, malonic, glutaric or tartaric acids.
- metal carboxylate salts is also meant to include carboxylic acids which are capable of forming carboxylate salts in situ under conditions including the presence of a base and a metal ion, and compounds which are capable of forming carboxylic or carboxylate groups in situ, including, e.g., esters, lactones, anhydrides and amides.
- amine-containing compound a compound capable of producing a metal-amine complex when metal salts react with amines under basic conditions.
- amine-containing compounds include ammonium hydroxide, ammonia, and aliphatic, aromatic and heteroaromatic amines.
- a filter having pores is provided, the filter is contacted with an activator, the filter is dried, and the dried filter is contacted with a metal salt or metal carboxylate salt solution so as to deposit the metal on the surface and within a plurality of the pores of the filter.
- the activator is a salt of a metal including, e.g., tin, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, germanium, selenium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, antimony, tellurium and lead.
- a preferred activator is tin dichloride.
- An alternative embodiment is to contact the dried filter with an amine containing compound in addition to the metal salt or metal carborylate salt solution.
- metals can be electroplated onto the surface of suitably primed polymeric materials using standard well known techniques. It is necessary to prime the polymer surface to allow for the electroplating process to occur because most polymers are electrically insulating and do not carry an electrical current. Priming deposits a very small amount of metal onto the surface of the polymer allowing for the subsequent electrolytic deposition of a metal from solution.
- the metal coating on the filters derived from any of the methods discussed above, can be further treated to produce a metal oxide coating, as described in Example 7.
- This invention also includes the products made in accordance with these methods.
- This invention also provides a method for dispensing sterile liquid by applying pressure to the container of the liquid dispenser of this invention so as to discharge the sterile liquid from the container.
- the container has an elastically deformable wall, pressure is applied to deform the wall and force the sterile liquid from the container through the filter, and the wall is allowed to recover so as to draw gas from the surrounding atmosphere into the container, the gas being sterilized as it passes through the filter.
- the liquid dispenser can be used for any purpose which requires dispensing a sterile solution from a container.
- uses include, e.g., medical related purposes, e.g., dispensing sterile liquids onto any part of the body of an organism or onto an object that is to be placed into the body of an organism, e.g, for use in eye, ear, or nose care.
- this invention provides a method for using the liquid dispenser of this invention for eyecare in an organism in which a sterile eyecare liquid is dispensed into an eye of the organism or onto an object that is to be placed into the eye of the organism.
- the sterile eyecare liquid is preservative-free.
- the sterile eyecare liquid includes, e.g., liquid artificial tears, a solution for contact lens care or a medicament.
- medicaments are antibiotics, decongestants, anti-inflammatories, anti-glaucoma agents, anti-bacterial agents, anti-viral agents, anesthetics, mydriatics, anti-cholingerics and miotics.
- An object that is to be placed into the eye includes, e.g., a contact lens.
- process filters for sterilization of all types of solutions e.g., drug solutions and instillation solutions
- intravenous catheters where a membrane unit is employed for the admittance of air but prevents back flow of blood or other liquids
- process filters for food products where sterility is required
- dispensation of items such as baby formula where the presence of a preservative would be undesirable
- membrane filter units e.g., for campers and hikers where the generation of microbial free water is desired without the possibility of future contamination.
- MMD Metal Vapor Deposition
- This example illustrates a method for depositing silver onto a surface, but not within the pores, of a membrane filter.
- a precut polyethersulfone membrane (Supor 400, pore size 0.45 ⁇ M, hydrophilic) (obtained from Gelman of Ann Arbor, Mich.) was mounted on a plate such that the surface to be coated faced the heating source of a metal evaporator.
- An approximately 4-6 inch long silver wire (obtained from Johnson Matthey of Wardhill, Mass.) was rolled into a coil and placed on the metal bridge in the evaporator. The evaporator was pumped down to 10 -5 Torr and a current of approximately 60-70 amperes was applied to melt the silver.
- a uniform silver coating of the membrane surface resulted in about 15-30 secs.
- the current was turned off and the evaporator chamber was allowed to return to atmospheric pressure.
- the membrane was turned over and the procedure repeated.
- the resulting membrane had a uniform coating of silver on both surfaces, but not within the pores, as determined by scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX).
- This example illustrates a method for depositing metallic silver onto a surface, and within the pores, of a membrane filter.
- a polyethersulfone membrane (Supor 400, pore size 0.45 ⁇ M, hydrophilic) (Gelman) was precut into a 47 mm disk. This membrane was immersed in 5 ml of glutaraldehyde (25% solution) (obtained from Aldrich of Milwaukee, Wis.) for 1 min. at 22° C., removed from the aldehyde solution and air dried thoroughly. The treated membrane was then immersed in 5 ml of the silver coating solution described in Example 6A, at pH approximately 12 (the pH can range from approximately 8-14), at 35° C. for 15 secs. The plated membrane was thoroughly rinsed with distilled water and dried in a vacuum oven at 20° C. for 2 hrs. SEM coupled with EDX showed uniform silver coating on the membrane surface and within the pores.
- This example illustrates a method for depositing metallic silver onto a surface and within the pores of a membrane filter.
- a polyethersulfone membrane (Millipore, pore size 0.45 ⁇ M, hydrophobic) (obtained from Millipore Corp. of Bedford, Mass.), was precut into a 47 mm disk.
- This membrane was immersed in 5 ml of 0.1M ⁇ -D-glucose in an aqueous solution containing 10% ethanol for 5 mins. at 22° C., removed from the sugar solution and air dried throughly.
- the treated membrane was then immersed in 5 ml of the silver coating solution described in Example 6A, at pH approximately 12 at 35° C. for 2 mins.
- the plated membrane was thoroughly rinsed with distilled water and dried in a vacuum oven at 20° C. for 2 hrs. SEM coupled with EDX showed uniform silver coating on the membrane surface and within the pores.
- This example illustrates a method for depositing metallic silver onto a surface and within the pores of a membrane filter.
- a polyethersulfone membrane (Gelman Supor 400, pore size 0.45 ⁇ M, hydrophilic) was precut into a 47 mm disk. This membrane was immersed in 5 ml of the silver coating solution described in Example 6B, which was then heated to 55° C. and maintained at this temperature for 5 mins. The plated membrane was thoroughly rinsed with distilled water and dried in a vacuum oven at 20° C. for 2 hrs. SEM coupled with EDX showed uniform silver coating on the membrane surface and within the pores.
- This example illustrates a method for depositing metallic silver onto a surface and within the pores of a membrane filter.
- a polyethersulfone membrane (Gelman Supor 400, pore size 0.45 ⁇ M, hydrophilic) was precut into a 47 mm disk. This membrane was immersed in 5 ml of a solution containing 1 g tin dichloride, 1 ml concentrated HCl and 9 ml distilled water, at room temperature for 5 mins. The membrane was dried and immersed in the silver coating solution, described in Example 6B, which was then heated to 55° C. and maintained at this temperature for 3 mins. A rapid deposition of metallic silver on the membrane surface ensued. The plated membrane was thoroughly rinsed with distilled water and dried in a vacuum oven at 20° C. SEM coupled with EDX showed uniform silver coating on the membrane surface and within the pores.
- Salts of other metals including titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, germanium, selenium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, antimony, tellurium and lead may be used as activators in place of tin dichloride prior to silver plating.
- This example illustrates a method for treating a silver coated membrane filter with oxygen plasma so as to produce a silver oxide coating.
- a silver coated polyethersulfone membrane obtained from either Example 1 or 2, was mounted on a glass holder and placed inside the reaction chamber of a plasma reactor so that both surfaces of the filter were exposed to the plasma.
- the reaction chamber was purged with oxygen three times.
- the pressure of the chamber was adjusted to 300 mTorr, the power maintained at 100 watts, and the membrane subjected to oxygen plasma for 2 mins.
- This example illustrates a method for treating a silver coated membrane filter with a second compound that has anti-bacterial or anti-viral properties.
- a freshly silver coated polyethersulfone membrane obtained from Example 1 or 2 was immersed in this solution at 22° C. for 16 hrs, rinsed in absolute ethanol, and dried under a stream of nitrogen.
- This example illustrates a method for the synthesis of BAC-S from 10-chlorodecanethiol which in turn is synthesized from ⁇ -chlorodecanethioacetate.
- Triphenylphosphine (6.53 g, 25 mmol) (obtained from Aldrich) was dissolved in 95 ml of dry, distilled tetrahydrofuran and the solution was cooled to 0° C. under dry nitrogen. 4.9 ml (25 mmol) of di-isopropylazodicarbonate (obtained from Aldrich) was added to the solution. The reaction mixture was stirred for 30 min. at 0° C. during which time a white precipitate formed. A 1M solution of 10-chloro-1-decanol (4.82 g in 25 ml THF (tetrahydrofuran) (obtained from VWR Scientific of Boston, Mass.) was added.
- This example illustrates a method for depositing silver onto the inner surface of tubing which can be used for the passageway walls in the nozzle assembly of the liquid dispenser.
- Polyethylene tubing (2 inches long, 800 ⁇ M ID) (obtained from Putnam Plastics Corp. of Dayville, Conn.) was immersed in a 25% aq. glutaraldehyde solution and ultrasonicated at 20° C. for 2 mins. The tubing was then dried thoroughly and silver coating solution, as described in Example 6A, was drawn into the tubing with a pipette. The plating solution was allowed to soak inside the tubing for 3 mins at 20° C., the excess solution was then expelled and the inside of the tubing was flushed with distilled water. A uniform silver coating resulted on the inside surface of the tubing.
- the tubing was tested for bacteriocidal activity.
- Control or silver treated plastic tubing was inoculated with 10 ⁇ ls of a suspension of Pseudomonas dimunata containing 5 ⁇ 10 7 organisms.
- the tubes containing bacterial suspension were incubated 15 hours at 37° C., at which time the tubes were placed in thioglycollate bacterial culture medium (1 cc) and vortexed. Aliquots of this solution were removed and serially diluted and 100 ⁇ ls of these dilutions were plated onto NZY agar plates. The plates were incubated overnight at 37° C. and the bacterial concentrations were determined by counting bacterial colonies.
- This example illustrates a method for producing a silver coated membrane filter that is partially hydrophobic and partially hydrophilic.
- 20.2 mg (20 mmol) of 1-dodecanethiol obtained from Sigma Chemical Co., St. Louis, Mo.
- a freshly silver coated (by MVD or electroless process) polyethersulfone membrane (Gelman Supor 400, pore size 0.45 ⁇ M, hydrophilic) was partially immersed in this solution at 22° C. for 16 hours.
- the membrane was then rinsed in absolute ethanol and dried under a stream of nitrogen.
- the resulting surface treated membrane was hydrophobic (non-wetting) in the area treated with the alkyl thiol while remaining hydrophilic in the non-treated area.
- This example illustrates a method for depositing metallic silver onto the surface of PMMA sheets.
- a commercially obtained PMMA sheet was cut in the form of a slide and the surface was cleaned by ultrasonication in absolute ethanol for 1 minute at room temperature.
- the cleaned slide was then immersed in 30 ml of an activator solution consisting of 10% tin dichloride dihydrate (SnCl 2 2H 2 O) (obtained from Allied Chemicals of New York, N.Y.), 45% absolute ethanol and 45% distilled water and ultrasonicated at 45° C. for 15 minutes.
- the slide was then rinsed several times with distilled water. It was then immersed in a 10% aqueous solution of silver nitrate for 15 minutes at room temperature. During this time the slide acquired a brown tinge due to the deposition of silver.
- the coated slide was then rinsed with distilled water and dried. The silver coating was adherent to the polymer and did not cause loss of transparency of the slide.
- This example illustrates a method for depositing a metallic silver coating onto the surface of polypropylene slides (obtained from Eastman Chemical Product, Inc., Kingsport, Tenn.).
- the slides were immersed in 30 ml of a 5% solution of chlorosulfonic acid (obtained from Aldrich of Milwaukee, Wis.) in chloroform at 50° C. for 5 mins. They were allowed to dry for 15 mins. then immersed in a 1M aqueous solution of sodium hydroxide after which they were rinsed thoroughly with distilled water.
- the surface treated slides were subjected to the silver coating procedure described in Example 4 using the plating solution described in Example 6B. This resulted in a uniform silver coating that is adherent to the polypropylene surface.
- This example illustrates a method for testing different types of membrane filters with different pore sizes, which have been coated with different compounds by different procedures, for their bacteriocidal/bacteriostatic properties.
- the challenge organism either Pseudomonas dimunata, or a cocktail of Pseudomonas dimunata, Bacillus subtilis, Bacillus vulgaris and Escherichia coli, at a concentration of 10 7 organisms per ml, was purged through the filter using a 3 cc syringe and manual pressure. Approximately 1 cc of liquid was expelled first and was checked for sterility so to ensure that the membrane was properly sealed. Three drops of eluate were collected and tested for sterility. The outlet tip was maintained in a sterile environment using a clean sterile cover and the entire unit was stored at 37° C. for the course of the experiment.
- the sterility of the eluate was tested daily by collecting three drops (approximately 150 ⁇ l) of bacteria/media inoculum into sterile thioglycollate medium which was then placed in a 37° C. shaker overnight and assessed the next day for sterility. As the medium/bacteria inoculum level lowered over the course of the experiment, the input syringe was removed end fresh sterile media was added and reattached to the filter holder unit. A filter was considered to have "failed" when the sterility check failed on two consecutive tests, the failed filter apparatus still held air pressure under water, and the failed sterility check demonstrated by gram stain the expected morphology of the test organism.
- GS Gelman Supor 400 membranes
- GH Gelman HT650 membranes
- M Millipore membranes.
- the type of material that the membranes are composed of is indicated by “PES” for polyethersulfone and “PVDF” for polyvinylidene fluoride.
- ⁇ M indicates the micron pore size of the membrane.
- - indicates that the membrane was untreated.
- MVDAg indicates the membrane was treated to produce a silver coating by the metal vapor deposition method as described in Example 1.
- TAg indicates the membrane was treated to produce a silver coating by the electroless method of this invention as described in Example 2, Method 1.
- the numbers in the "Days” column indicate the average number of days until the filter failed, as determined by the criteria discussed above.
- a ">#” indicates that no failure was detected for the duration of the test, i.e., the number of days indicated.
Abstract
Description
TABLE 1 ______________________________________ Bacterial Challenge Experiments on Silver Coated Membranes Growth Steril- Mfgr Type mM Treatment Days Medium ization No. ______________________________________ GS PES 0.45 -- 7B A 3 GS PES 0.45 MVDAg +P 10B A 3 GS PES 0.45TAg 22B A 3 GS PES 0.45 TAg +P 16B A 3 GS PES 0.45 MVDAg +B 14B A 3 GS PES 0.45 TAg + B >77B A 3 GS PES 0.45 -- 7B A 9 GS PES 0.45 TAg >25B A 6 GS PES 0.45 -- 10T A 9 GS PES 0.45 TAg >76T A 9 GS PES 0.45 -- 3S A 6 GS PES 0.45 TAg >43S A 6 ______________________________________
Claims (5)
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US08/599,810 US5681468A (en) | 1993-12-20 | 1996-02-12 | Filter coated with antimicrobial material |
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US08/170,510 US5490938A (en) | 1993-12-20 | 1993-12-20 | Liquid dispenser for sterile solutions |
US08/599,810 US5681468A (en) | 1993-12-20 | 1996-02-12 | Filter coated with antimicrobial material |
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US08/170,510 Division US5490938A (en) | 1993-12-20 | 1993-12-20 | Liquid dispenser for sterile solutions |
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US5681468A true US5681468A (en) | 1997-10-28 |
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US08/170,510 Expired - Lifetime US5490938A (en) | 1993-12-20 | 1993-12-20 | Liquid dispenser for sterile solutions |
US08/599,810 Expired - Fee Related US5681468A (en) | 1993-12-20 | 1996-02-12 | Filter coated with antimicrobial material |
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US20130220905A1 (en) * | 2012-02-23 | 2013-08-29 | Infinite Water, Inc. | Water Production, Filtration and Dispensing System |
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Families Citing this family (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0735852B1 (en) * | 1993-12-20 | 1999-09-22 | Biopolymerix, Inc. | Liquid dispenser for sterile solutions |
US5490938A (en) * | 1993-12-20 | 1996-02-13 | Biopolymerix, Inc. | Liquid dispenser for sterile solutions |
US5817325A (en) * | 1996-10-28 | 1998-10-06 | Biopolymerix, Inc. | Contact-killing antimicrobial devices |
US5814164A (en) | 1994-11-09 | 1998-09-29 | American Scientific Materials Technologies L.P. | Thin-walled, monolithic iron oxide structures made from steels, and methods for manufacturing such structures |
FR2736285B1 (en) * | 1995-07-07 | 1997-08-22 | Valois | DEVICE FOR DISPENSING FLUID PRODUCT WITH BACTERIOSTATIC ACTION |
FR2746657B1 (en) * | 1996-03-29 | 1998-06-26 | Sofab | ANTIBACTERIAL DEVICE FOR SPRAYING A LIQUID PRODUCT |
FR2751882B1 (en) * | 1996-07-31 | 1998-10-02 | Inst Curie | HYPERBACTERICIDAL SURFACES |
FR2761665B1 (en) * | 1997-04-02 | 1999-06-25 | Sofab | DEVICE FOR DISPENSING AND PACKAGING STERILE LIQUID PRODUCTS |
GB2365511B (en) * | 1997-07-16 | 2002-03-27 | Pall Corp | Valves for filters |
US6053369A (en) * | 1998-09-28 | 2000-04-25 | Becton Dickinson And Company | Foam forming liquid dispensing device |
US6461562B1 (en) | 1999-02-17 | 2002-10-08 | American Scientific Materials Technologies, Lp | Methods of making sintered metal oxide articles |
US7232433B1 (en) | 1999-09-22 | 2007-06-19 | Siemens Medical Solutions Usa, Inc. | Medical diagnostic ultrasound catheter with dielectric isolation |
EP1322407A4 (en) * | 2000-09-05 | 2004-07-28 | Miox Corp | Reverse osmosis membrane and process for making same |
JP4580524B2 (en) * | 2000-09-12 | 2010-11-17 | 株式会社日本点眼薬研究所 | Discharge container with filter |
BR0107882A (en) | 2000-11-30 | 2002-11-05 | Cebal | Containers that have a wall containing biocidal agents |
US6463695B2 (en) * | 2001-03-22 | 2002-10-15 | Mcdonough John P. | Liquid bait station |
FR2830240B1 (en) * | 2001-10-01 | 2004-08-20 | Oreal | DEVICE FOR PACKAGING A PRODUCT, IN PARTICULAR A COSMETIC AND / OR CARE PRODUCT |
US6766816B2 (en) * | 2001-10-03 | 2004-07-27 | Hunter Group, Inc. | Collapsible dispensing system |
US6835311B2 (en) * | 2002-01-31 | 2004-12-28 | Koslow Technologies Corporation | Microporous filter media, filtration systems containing same, and methods of making and using |
EP1495747B1 (en) * | 2002-04-04 | 2013-01-16 | Nipro Corporation | Liquid drug container |
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US7767217B2 (en) | 2006-03-14 | 2010-08-03 | Foresight Biotherapeutics | Ophthalmic compositions comprising povidone-iodine |
JP4869039B2 (en) * | 2006-11-27 | 2012-02-01 | ニプロ株式会社 | Chemical container |
WO2009097123A1 (en) * | 2008-01-28 | 2009-08-06 | Foresight Biotherapeutics, Inc. | Device for in-situ generation of povidone-iodine compositions |
FR2954327B1 (en) * | 2009-12-23 | 2012-11-30 | Valois Sas | METHOD FOR SURFACE TREATMENT OF A FLUID PRODUCT DISPENSING DEVICE |
US9283333B2 (en) * | 2010-07-16 | 2016-03-15 | Boehringer Ingelheim International Gmbh | Filter system for use in medical devices |
EP2458346B1 (en) * | 2010-11-29 | 2013-06-19 | Mettler-Toledo AG | Metering unit for dosing material in powder or granular form |
WO2013011511A1 (en) | 2011-07-18 | 2013-01-24 | Mor Research Applications Ltd. | A device for adjusting the intraocular pressure |
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US9421199B2 (en) | 2014-06-24 | 2016-08-23 | Sydnexis, Inc. | Ophthalmic composition |
WO2016172712A2 (en) | 2015-04-23 | 2016-10-27 | Sydnexis, Inc. | Ophthalmic composition |
US11382909B2 (en) | 2014-09-05 | 2022-07-12 | Sydnexis, Inc. | Ophthalmic composition |
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CN107847432A (en) | 2015-05-29 | 2018-03-27 | 西德奈克西斯公司 | D2The stabilized pharmaceutical preparations of O |
MX2020005217A (en) * | 2017-11-21 | 2020-11-24 | Sydnexis Inc | Ophthalmic composition and delivery device thereof. |
WO2021091402A1 (en) * | 2019-11-05 | 2021-05-14 | Gamboa Burgos Alejandro | Kit for ophthalmic solutions in screw-cap drop bottles |
US11825974B1 (en) * | 2020-03-01 | 2023-11-28 | Michael O. Murphy | Expandable strainer insert for bottles |
Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3909200A (en) * | 1967-05-22 | 1975-09-30 | Petrolite Corp | Use of guanidine derived compounds as corrosion inhibitors |
US4470859A (en) * | 1981-06-26 | 1984-09-11 | Diamond Shamrock Chemicals Company | Coated porous substrate formation by solution coating |
US4563485A (en) * | 1984-04-30 | 1986-01-07 | The Trustees Of Columbia University In The City Of New York | Injection-resistant materials and method of making same through use of nalidixic acid derivatives |
US4581028A (en) * | 1984-04-30 | 1986-04-08 | The Trustees Of Columbia University In The City Of New York | Infection-resistant materials and method of making same through use of sulfonamides |
US4592920A (en) * | 1983-05-20 | 1986-06-03 | Baxter Travenol Laboratories, Inc. | Method for the production of an antimicrobial catheter |
US4603152A (en) * | 1982-11-05 | 1986-07-29 | Baxter Travenol Laboratories, Inc. | Antimicrobial compositions |
US4612337A (en) * | 1985-05-30 | 1986-09-16 | The Trustees Of Columbia University In The City Of New York | Method for preparing infection-resistant materials |
US4675347A (en) * | 1983-10-29 | 1987-06-23 | Unitika Ltd. | Antimicrobial latex composition |
US4677143A (en) * | 1984-10-01 | 1987-06-30 | Baxter Travenol Laboratories, Inc. | Antimicrobial compositions |
US4769013A (en) * | 1982-09-13 | 1988-09-06 | Hydromer, Inc. | Bio-effecting medical material and device |
US4853978A (en) * | 1987-07-24 | 1989-08-08 | Surgikos, Inc. | Antimicrobial medical glove |
US5019096A (en) * | 1988-02-11 | 1991-05-28 | Trustees Of Columbia University In The City Of New York | Infection-resistant compositions, medical devices and surfaces and methods for preparing and using same |
US5167820A (en) * | 1986-03-24 | 1992-12-01 | Ensci, Inc. | Porous membranes and methods for using same |
US5490938A (en) * | 1993-12-20 | 1996-02-13 | Biopolymerix, Inc. | Liquid dispenser for sterile solutions |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4150171A (en) * | 1976-03-30 | 1979-04-17 | Surface Technology, Inc. | Electroless plating |
JPS5513778A (en) * | 1978-04-26 | 1980-01-30 | Smith & Nephew Pharma | Water soluble polymer*sterilization*and disinfectant colution |
US4533068A (en) * | 1981-08-17 | 1985-08-06 | Health Care Concepts, Inc. | Sterile solution delivery and venting devices |
US4463880A (en) * | 1982-04-30 | 1984-08-07 | The Regents Of The University Of California | Medicine drop dispenser with anti-bacterial filter |
US4494663A (en) * | 1984-01-05 | 1985-01-22 | Abbott Laboratories | Sterile solution container |
FR2558485B1 (en) * | 1984-01-25 | 1990-07-13 | Rech Applic Electrochimique | POROUS METAL STRUCTURE, MANUFACTURING METHOD THEREOF AND APPLICATIONS |
JPS618104A (en) * | 1984-06-25 | 1986-01-14 | Mitsubishi Rayon Co Ltd | Sterilizable porous polyolefin hollow yarn |
GB8720502D0 (en) * | 1987-08-29 | 1987-10-07 | Giltech Ltd | Antimicrobial composition |
JPH0268105A (en) * | 1988-09-02 | 1990-03-07 | Ind Res Inst Japan | Filtration membrane having antibiotic action |
US5060823A (en) * | 1988-09-15 | 1991-10-29 | Brandeis University | Sterile transfer system |
JPH02192937A (en) * | 1988-10-04 | 1990-07-30 | Toppan Printing Co Ltd | Manufacture of antibacterial film |
US4917271A (en) * | 1988-10-07 | 1990-04-17 | Ryder International Corporation | Liquid dispensing nozzle assembly with filter |
US5025957A (en) * | 1988-10-07 | 1991-06-25 | Ryder International Corp. | Liquid dispenser nozzle assembly |
US4938389A (en) * | 1988-11-03 | 1990-07-03 | Eye Research Institute Of Retina Foundation | Filter bottle |
US5040706A (en) * | 1989-03-17 | 1991-08-20 | Insite Vision, Inc. | Liquid droplet dispensing apparatus |
US5265770A (en) * | 1989-06-01 | 1993-11-30 | Pall Corporation | Contamination-resistant dispensing and metering device |
JPH03143535A (en) * | 1989-10-26 | 1991-06-19 | Toto Ltd | Asymmetric ceramic film and production thereof |
US5105993A (en) * | 1989-12-29 | 1992-04-21 | La Haye Laboratories, Inc. | Disposable medical dispenser with a filtering dispenser nozzle |
US5074440A (en) * | 1990-07-16 | 1991-12-24 | Alcon Laboratories, Inc. | Container for dispensing preservative-free preparations |
JPH04197362A (en) * | 1990-11-29 | 1992-07-16 | Furukawa Electric Co Ltd:The | Manufacture of catheter |
JPH04197363A (en) * | 1990-11-29 | 1992-07-16 | Furukawa Electric Co Ltd:The | Manufacture of catheter |
US5510195A (en) * | 1991-03-01 | 1996-04-23 | Nikko Kogyo Kabushiki Kaisha | Resin membrane having metallic layer and method of producing the same |
-
1993
- 1993-12-20 US US08/170,510 patent/US5490938A/en not_active Expired - Lifetime
-
1996
- 1996-02-12 US US08/599,810 patent/US5681468A/en not_active Expired - Fee Related
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3909200A (en) * | 1967-05-22 | 1975-09-30 | Petrolite Corp | Use of guanidine derived compounds as corrosion inhibitors |
US4470859A (en) * | 1981-06-26 | 1984-09-11 | Diamond Shamrock Chemicals Company | Coated porous substrate formation by solution coating |
US4769013A (en) * | 1982-09-13 | 1988-09-06 | Hydromer, Inc. | Bio-effecting medical material and device |
US4603152A (en) * | 1982-11-05 | 1986-07-29 | Baxter Travenol Laboratories, Inc. | Antimicrobial compositions |
US4592920A (en) * | 1983-05-20 | 1986-06-03 | Baxter Travenol Laboratories, Inc. | Method for the production of an antimicrobial catheter |
US4675347A (en) * | 1983-10-29 | 1987-06-23 | Unitika Ltd. | Antimicrobial latex composition |
US4581028A (en) * | 1984-04-30 | 1986-04-08 | The Trustees Of Columbia University In The City Of New York | Infection-resistant materials and method of making same through use of sulfonamides |
US4563485A (en) * | 1984-04-30 | 1986-01-07 | The Trustees Of Columbia University In The City Of New York | Injection-resistant materials and method of making same through use of nalidixic acid derivatives |
US4677143A (en) * | 1984-10-01 | 1987-06-30 | Baxter Travenol Laboratories, Inc. | Antimicrobial compositions |
US4612337A (en) * | 1985-05-30 | 1986-09-16 | The Trustees Of Columbia University In The City Of New York | Method for preparing infection-resistant materials |
US5167820A (en) * | 1986-03-24 | 1992-12-01 | Ensci, Inc. | Porous membranes and methods for using same |
US5269935A (en) * | 1986-03-24 | 1993-12-14 | Ensci Inc. | Porous membranes and methods for using same |
US4853978A (en) * | 1987-07-24 | 1989-08-08 | Surgikos, Inc. | Antimicrobial medical glove |
US5019096A (en) * | 1988-02-11 | 1991-05-28 | Trustees Of Columbia University In The City Of New York | Infection-resistant compositions, medical devices and surfaces and methods for preparing and using same |
US5490938A (en) * | 1993-12-20 | 1996-02-13 | Biopolymerix, Inc. | Liquid dispenser for sterile solutions |
Cited By (81)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6180584B1 (en) * | 1998-02-12 | 2001-01-30 | Surfacine Development Company, Llc | Disinfectant composition providing sustained residual biocidal action |
US6995853B1 (en) | 2000-03-31 | 2006-02-07 | Pitney Bowes Inc. | Method and system for modifying print stream data to allow printing over a single I/O port |
US7655112B2 (en) * | 2002-01-31 | 2010-02-02 | Kx Technologies, Llc | Integrated paper comprising fibrillated fibers and active particles immobilized therein |
US20040031749A1 (en) * | 2002-01-31 | 2004-02-19 | Koslow Evan E. | Structures that inhibit microbial growth |
US7287650B2 (en) * | 2002-01-31 | 2007-10-30 | Kx Technologies Llc | Structures that inhibit microbial growth |
US20040178142A1 (en) * | 2002-01-31 | 2004-09-16 | Koslow Evan E. | Integrated paper comprising fibrillated fibers and active particles immobilized therein |
US8056733B2 (en) | 2002-01-31 | 2011-11-15 | Kx Technologies Llc | Structures that inhibit microbial growth |
US20100044289A1 (en) * | 2002-01-31 | 2010-02-25 | Kx Technologies Llc | Integrated Paper Comprising Fibrillated Fibers and Active Agents Immobilized Therein |
US20070298064A1 (en) * | 2002-01-31 | 2007-12-27 | Kx Technologies Llc | Structures that inhibit microbial growth |
US8613363B2 (en) | 2002-01-31 | 2013-12-24 | Kx Technologies Llc | Integrated paper comprising fibrillated fibers and active agents immobilized therein |
US20040154972A1 (en) * | 2002-02-13 | 2004-08-12 | Cho Steven T. | Micro-fluidic anti-microbial filter |
US7201846B2 (en) * | 2002-02-13 | 2007-04-10 | Hospira, Inc. | Micro-fluidic anti-microbial filter |
KR100445797B1 (en) * | 2002-02-28 | 2004-08-25 | 토리 주식회사 | Sterilized multi-functional filter and manufacturing method thereof |
US7160272B1 (en) | 2002-05-31 | 2007-01-09 | Elcam Plastic | Y-site medical valve |
US20040129648A1 (en) * | 2002-07-23 | 2004-07-08 | Manesis Nick J. | Antimicrobial matrix and method of use |
US20060149212A1 (en) * | 2002-07-23 | 2006-07-06 | Manesis Nick J | Antimicrobial matrix and method of use |
US20050051487A1 (en) * | 2002-11-01 | 2005-03-10 | Koslow Evan E. | Fiber-fiber composites |
US7276166B2 (en) * | 2002-11-01 | 2007-10-02 | Kx Industries, Lp | Fiber-fiber composites |
EP1628922A4 (en) * | 2003-04-11 | 2011-02-23 | Kx Technologies Llc | Microporous filter media with intrinsic safety feature |
WO2004092076A1 (en) | 2003-04-11 | 2004-10-28 | Koslow Technologies Corporation | Microporous filter media with intrinsic safety feature |
EP1628922A1 (en) * | 2003-04-11 | 2006-03-01 | Koslow Technologies Corporation | Microporous filter media with intrinsic safety feature |
US8425926B2 (en) | 2003-07-16 | 2013-04-23 | Yongxing Qiu | Antimicrobial medical devices |
US20050013842A1 (en) * | 2003-07-16 | 2005-01-20 | Yongxing Qiu | Antimicrobial medical devices |
US20050011827A1 (en) * | 2003-07-18 | 2005-01-20 | Koslow Evan E. | Carbon or activated carbon nanofibers |
US7296691B2 (en) * | 2003-07-18 | 2007-11-20 | Kx Technologies Llc | Carbon or activated carbon nanofibers |
US20080197069A1 (en) * | 2003-08-01 | 2008-08-21 | Olaf Binkle | Ceramic Filter Element for Water Purification |
EP1683737A4 (en) * | 2003-11-11 | 2008-09-03 | Taisei Kako Co | Filter-equipped container |
WO2005044689A1 (en) | 2003-11-11 | 2005-05-19 | Taisei Kako Co., Ltd. | Filter-equipped container |
EP1683737A1 (en) * | 2003-11-11 | 2006-07-26 | Taisei Kako Co., Ltd. | Filter-equipped container |
US20050249818A1 (en) * | 2004-05-03 | 2005-11-10 | Sawan Samuel P | Polycationic antimicrobial therapeutic |
US20060091063A1 (en) * | 2004-11-03 | 2006-05-04 | Paterson Graham H | Anti-contamination inlet screen for automatic faucets |
WO2007075686A1 (en) * | 2005-12-22 | 2007-07-05 | Bausch & Lomb Incorporated | Antimicrobial ophthalmic treatment system and method |
US20070148127A1 (en) * | 2005-12-22 | 2007-06-28 | Heiler David J | Antimicrobial ophthalmic treatment system and method |
US20080306301A1 (en) * | 2006-07-26 | 2008-12-11 | Water Visions International, Inc. | Broad spectrum antimicrobial purification materials and methods for purifying fluids |
US20080272062A1 (en) * | 2006-07-26 | 2008-11-06 | Water Visions International, Inc. | Broad spectrum antimicrobial purification devices and methods for purifying fluids |
US20080181931A1 (en) * | 2007-01-31 | 2008-07-31 | Yongxing Qiu | Antimicrobial medical devices including silver nanoparticles |
US20100044321A1 (en) * | 2007-03-09 | 2010-02-25 | Mikkel Vestergaard Frandsen | Microporous filter with a low elution antimicrobal source |
US20100051527A1 (en) * | 2007-03-09 | 2010-03-04 | Mikkel Vestergaard Frandsen | Microporous filter with an antimicrobial source |
US20080302713A1 (en) * | 2007-06-05 | 2008-12-11 | Gilbert Patrick | Antimicrobial filter cartridge |
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US20110020497A1 (en) * | 2008-01-24 | 2011-01-27 | Nestec S.A. | Capsule containing nutritional ingredients and method of delivery of a nutritional liquid from the capsule |
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WO2015197847A1 (en) * | 2014-06-27 | 2015-12-30 | Albea Services | Container and distributor head for such a container having a disinfectant effect |
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WO2016156897A1 (en) * | 2015-03-31 | 2016-10-06 | Laboratoires Thea | Device for dispensing liquid from a sterile packaging bottle with bifunctional membrane |
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CN107531370B (en) * | 2015-03-31 | 2019-07-19 | 希亚实验室公司 | The liquid dispensing apparatus of sterile packaging bottle |
CN107531370A (en) * | 2015-03-31 | 2018-01-02 | 希亚实验室公司 | The liquid dispensing apparatus of sterile packaging bottle |
US10857067B2 (en) | 2015-03-31 | 2020-12-08 | Laboratories Thea | Device for dispensing liquid from a sterile packaging bottle with bi-functional membrane |
KR20170133411A (en) * | 2015-03-31 | 2017-12-05 | 라보라토이레스 테아 | Apparatus for draining liquid from a sterile packaging container |
US11116694B2 (en) | 2015-03-31 | 2021-09-14 | Laboratories Thea | Device for dispensing liquid from a sterile packaging bottle |
WO2016156968A1 (en) | 2015-03-31 | 2016-10-06 | Laboratoires Thea | Device for dispensing liquid from a sterile packaging bottle |
TWI720025B (en) * | 2016-09-26 | 2021-03-01 | 法商希亞實驗室 | Sterile liquid dispenser |
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